CN103289015B - The preparation method of quaternary phosphine salt type cationic starch - Google Patents
The preparation method of quaternary phosphine salt type cationic starch Download PDFInfo
- Publication number
- CN103289015B CN103289015B CN201210043878.4A CN201210043878A CN103289015B CN 103289015 B CN103289015 B CN 103289015B CN 201210043878 A CN201210043878 A CN 201210043878A CN 103289015 B CN103289015 B CN 103289015B
- Authority
- CN
- China
- Prior art keywords
- starch
- quaternary
- type cationic
- salt type
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
A kind of preparation method of quaternary phosphine salt type cationic starch, it is characterized in that: be for raw material with starch, quaternary alkylphosphonium salt monomer, acrylamide, carry out graft copolymerization under radical polymerization initiator or effects of ionizing radiation, by C-C key, quaternary alkylphosphonium salt Cationic functional groups is connected on starch polymer, prepares quaternary phosphine salt type cationic starch.Instead of by ehter bond, quaternary alkylphosphonium salt Cationic functional groups is connected on starch polymer.Prepare quaternary phosphine salt type cationic starch in the present invention, technique is simple, is easy to suitability for industrialized production.Quaternary alkylphosphonium salt is compared with quaternary ammonium salt, thermally-stabilised good, and anti-microbial property wants high about 100 times, strong with the binding ability of gegenion or group.Therefore, compared with existing quaternary ammonium cation starch, the Heat stability is good of quaternary phosphonium cation starch prepared by the present invention, high adsorption capacity.
Description
Technical field
The present invention relates to polymer modification, specifically a kind of preparation method of quaternary phosphine salt type cationic starch, on starch chain skeleton, be namely grafted with the starch product of side base with quaternary phosphine cation group and/or side chain.The cationic starch adopting this technology to produce can be applied to industry and the fields such as papermaking, weaving, chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry.
Background technology
Starch belongs to natural high moleculer eompound, is by the polysaccharide polymer of multiple glucose molecule condensation, can be synthesized by plant by photosynthesis.Starch is the nutrient stored in plant materials, and be stored in seed and stem tuber, the starch content in all kinds of plant is all higher.Naturally occurring starch is called ative starch, and the starch through physics, chemistry or biological method modification is called modified starch.In the numerous modified starch kind of cationic starch one large series products.
Cationic starch at present both at home and abroad in patent and open source literature is all on starch backbone, be connected with side base with quaternary ammonium cation and/or side chain substantially, then has no report about the starch be connected with on starch backbone with quaternary phosphine cationic side base and/or side chain.
The similar of quaternary alkylphosphonium salt is in quaternary ammonium salt, but You Yu Phosphonium atomic radius is larger than carbon atom, and polarized action is strong.Its thermostability is better than quaternary ammonium salt, and anti-microbial activity is also far above quaternary ammonium salt.
Summary of the invention
Object of the present invention provides the preparation method of quaternary phosphine salt type cationic starch just based on above-mentioned prior art situation, realize: one is chemical graft process, and one is radiation graft process by two kinds of approach.Be carry out graft copolymerization under radical polymerization initiator or effects of ionizing radiation, by C-C key, quaternary alkylphosphonium salt Cationic functional groups be connected on starch polymer, instead of by ehter bond, quaternary alkylphosphonium salt Cationic functional groups be connected on starch polymer.
The object of the invention is to be achieved through the following technical solutions: the preparation method of quaternary phosphine salt type cationic starch of the present invention, for raw material with starch, quaternary alkylphosphonium salt monomer, acrylamide, by chemical initiation grafting mode or radiation initiation grafting mode, prepare quaternary phosphine salt type cationic starch.
As follows by preparation method's concrete steps of chemical initiation grafting mode:
(1) take starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01 ~ 0.5/0.01 ~ 1/0.1 ~ 20; Take the radical polymerization initiator of Zhan quaternary alkylphosphonium salt monomer, acrylamide gross weight 0.1 ~ 3%;
(2) with water by starch pasting, after being cooled to normal temperature, adding quaternary alkylphosphonium salt monomer, acrylamide, stir, fill nitrogen deoxygenation; Then temperature controls, at 25 ~ 90 DEG C, to add radical polymerization initiator, reacts 0.5 ~ 10 hour;
(3) cool, obtain quaternary phosphine salt type cationic starch aqua; Further drying, obtains quaternary phosphine salt type cationic starch pulvis.
According to how many differences of solvent for use amount, described chemical graft method can also be further divided into the multiple implementation methods such as wet method, dry method, semidrying.Described wet method preparation process, is obtain monomer phase with water dissolution monomer, with water, starch pasting is obtained starch phase, is then evenly reacted with chemical initiator initiation grafting afterwards by two-phase mixtures; Or starch grafted monomer being directly dissolved in gelatinization mutually in, mix the reaction of rear chemical initiator initiation grafting.Described dry preparation process, is add monomer in a small amount of water or organic solvent, is then uniformly mixed together with starch, reacts with chemical initiator initiation grafting.Wet method preparation process is applicable to the situation that the finished product are aqua, and dry preparation process is applicable to the situation that the finished product are pulvis.Semidrying is the processing method between wet method and dry method.In chemical graft method provided by the present invention, according to the difference of institute's water consumption, also wet method, dry method, semidrying can be divided into.
As follows by preparation method's concrete steps of radiation initiation grafting mode:
(1) take starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01 ~ 0.5/0.01 ~ 1/0.1 ~ 20;
(2) with water by starch pasting, after being cooled to normal temperature, adding quaternary alkylphosphonium salt monomer, acrylamide, stir, fill nitrogen deoxygenation; Then radiation field irradiation is placed in, absorption dose 0.5 ~ 100KGy, preferably 0.5 ~ 50KGy.Described radiation field comprises gamma-radiation radiation field, electron beam irradiation field;
(3) take out in radiation chamber, obtain quaternary phosphine salt type cationic starch aqua; Further drying, obtains quaternary phosphine salt type cationic starch pulvis.
According to how many differences of solvent for use amount, described method for radio-grafting also can be further divided into the multiple implementation methods such as wet method, dry method, semidrying.Gamma-radiation or electron beam act on the water molecules in water solution system, and water molecules is stimulated or ionizes, and produce a large amount of Active Radicals Produced.These Free Radicals are in starch polymer, and can make starch polymer produces active site, monomer carries out chainpropagation at active site place, form grafted chain; These free radicals also can directly be polymerized by trigger monomer, form free macromolecular chain.Meanwhile, gamma-radiation or electron beam directly act on the starch in water solution system, make starch polymer direct ionization, and form active site, monomer carries out chainpropagation at active site place, form grafted chain.
Described in above-mentioned chemical graft and method for radio-grafting, quaternary alkylphosphonium salt monomer has general formula:
And/or
Wherein, n=1 ~ 20; R
1, R
2, R
3, R
4, R
5, R
6h, C independently of one another
1-C
40alkyl, aryl or heteroaryl; X represents halogen, comprises Cl or Br.A kind of in described quaternary alkylphosphonium salt monomer preferred allyl group trimethylammonium phosphonium halide, allyl group tributyl phosphonium halide, allyl group triphenyl phosphonium halide, vinylbenzyltrimethyl phosphonium halide, vinyl benzyl tributyl phosphonium halide, vinyl benzyl triphenyl phosphonium halide, or multiple.
In described chemical graft and method for radio-grafting, the Main Function of acrylamide is to improve the grafting efficiency of quaternary alkylphosphonium salt monomer on starch, therefore should select be easy on starch polymer grafting and also easily Yu the monomer of quaternary alkylphosphonium salt monomer copolymerization, can certainly.
Described in chemical graft method, radical polymerization initiator is persulphate, ceric ammonium nitrate, persulphate-sulphite.
Prepare quaternary phosphine salt type cationic starch in the present invention, technique is simple, is easy to suitability for industrialized production.Quaternary alkylphosphonium salt is compared with quaternary ammonium salt, thermally-stabilised good, and anti-microbial property wants high about 100 times, strong with the binding ability of gegenion or group.Therefore, compared with existing quaternary ammonium cation starch, the Heat stability is good of quaternary phosphonium cation starch prepared by the present invention, high adsorption capacity.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1:
Be dissolved in 120 ml distilled waters by 20 grams of native cornstarchs (water ratio 12.7%), 85 DEG C of gelatinization 30min, are chilled to room temperature, obtain starch phase.Under mechanical stirring, 12 grams of acrylamides, 8 grams of vinyl benzyl triphenyl phosphonium chlorides and 0.25 gram of ammonium persulphate are dissolved in 80 ml distilled waters, obtain monomer phase.0.10 gram of sodium bisulfite is dissolved with 10 ml distilled waters.Monomer is added to starch mutually in, fill nitrogen deoxygenation, stir, be warming up to 40 DEG C, drip sodium sulfite solution, drip off in half an hour, react 4 hours.Room temperature cools, and obtains the aqua of quaternary phosphine salt type cationic starch.With the product that acetone precipitation obtains, then precipitation is placed in loft drier and dries, put into the cooling of moisture eliminator room temperature, pulverize, cross 100 mesh sieves, packaging, namely obtains pulvis.
Get pulvis as crude product, wrap with the filter paper of extracting, be placed in Soxhlet extractor, with volume ratio be the acetone/glacial acetic acid mixed solvent of 1:1 as extractant, after extracting 18h, 50 DEG C of vacuum-dryings, to constant weight (about 12h), obtain sterling.
Get about sterling 1g (being accurate to 0.001), precise, is designated as m.Then be dissolved in 50ml deionized water and (can suitably heat), adopt Mohr's method (Fo Erhadefa or method also can be adopted to raise the administration of justice) to measure chloride ion content.Be calculated as follows cationic degree:
(formula 1)
CD=M×0.05×(V-V
0)/1000m
The molecular weight of M---quaternary alkylphosphonium salt in formula
0.05---the concentration of silver nitrate solution, mol/L
V---sample consumes the volume of silver nitrate solution, ml
V
0---blank test consumes the volume of silver nitrate solution, ml
The quality of m---sample, g
Replicate(determination) three times, last calculating mean value.CD=0.11mmol/g。
embodiment 2:
12 grams of acrylamides, 8 grams of allyl group tributyl phosphonium bromides and 0.1 gram of ceric ammonium nitrate are dissolved in 50 ml distilled waters, obtain monomer phase.Under agitation be added to by monomer in 30 g potato ative starchs (water ratio 11.4%), nitrogen filled protection, is warming up to 55 DEG C, reacts 3 hours.Be transferred in loft drier and dry, then put into the cooling of moisture eliminator room temperature, pulverize, cross 100 mesh sieves, packaging, namely obtains the pulvis of quaternary phosphine salt type cationic starch.
Get appropriate pulvis, extracting, pure system.Analyze by method described in embodiment 1, CD=0.08mmol/g.
embodiment 3:
Be dissolved in 60 ml distilled waters by 6 grams of native cornstarchs (water ratio 12.7%), 85 DEG C of gelatinization 30min, are chilled to room temperature.Under mechanical stirring, add 8 grams of acrylamides and 2 grams of allyl group tributyl phosphonium bromides.Stir.Be transferred in polyethylene bag, inflated with nitrogen excluding air, airtight sealing, be placed in the indoor irradiation of gamma-ray irradiation, absorption dose is 3kGy.Then, radiation chamber is shifted out.With the product that acetone precipitation obtains, be then placed in loft drier and dry, put into the cooling of moisture eliminator room temperature, pulverize, cross 100 mesh sieves, packaging, namely obtains the pulvis of quaternary phosphine salt type cationic starch.
Get appropriate pulvis, extracting, pure system.Analyze by method described in embodiment 1, CD=0.17mmol/g.
embodiment 4:
4 grams of acrylamides and 4 grams of vinyl benzyl tributyl phosphonium chlorides (77% pair of vinyl benzyl, 18% adjacent vinyl benzyl) are added, stirring and dissolving in 20 ml distilled waters.Then, under agitation the aqueous solution is joined in 10 grams of Zulkovsky starches, mix.Be transferred in polyethylene bag, inflated with nitrogen excluding air, airtight sealing, be placed in electron beam irradiation field irradiation, absorption dose is 5kGy.Then, radiation chamber is shifted out.
Get appropriate pulvis, extracting, pure system.Analyze by method described in embodiment 1, CD=0.15mmol/g.
Claims (5)
1. the preparation method of a quaternary phosphine salt type cationic starch, it is characterized in that: be for raw material with starch, quaternary alkylphosphonium salt monomer, acrylamide, by chemical initiation grafting mode or radiation initiation grafting mode, prepare quaternary phosphine salt type cationic starch, described quaternary alkylphosphonium salt monomer be in allyl group trimethylammonium phosphonium halide, allyl group tributyl phosphonium halide, allyl group triphenyl phosphonium halide, vinylbenzyltrimethyl phosphonium halide, vinyl benzyl tributyl phosphonium halide, vinyl benzyl triphenyl phosphonium halide one or more.
2. the preparation method of quaternary phosphine salt type cationic starch according to claim 1, is characterized in that: as follows by preparation method's concrete steps of chemical initiation grafting mode:
(1) take starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01 ~ 0.5/0.01 ~ 1/0.1 ~ 20; Take the radical polymerization initiator of Zhan quaternary alkylphosphonium salt monomer, acrylamide gross weight 0.1 ~ 3%;
(2) with water by starch pasting, after being cooled to normal temperature, adding quaternary alkylphosphonium salt monomer, acrylamide, stir, fill nitrogen deoxygenation; Then temperature controls, at 25 ~ 90 DEG C, to add radical polymerization initiator, reacts 0.5 ~ 10 hour;
(3) cool, obtain quaternary phosphine salt type cationic starch aqua; Further drying, obtains quaternary phosphine salt type cationic starch pulvis.
3. the preparation method of quaternary phosphine salt type cationic starch according to claim 1, is characterized in that: as follows by preparation method's concrete steps of radiation initiation grafting mode:
(1) take starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01 ~ 0.5/0.01 ~ 1/0.1 ~ 20;
(2) with water by starch pasting, after being cooled to normal temperature, adding quaternary alkylphosphonium salt monomer, acrylamide, stir, fill nitrogen deoxygenation; Then radiation field irradiation is placed in, absorption dose 0.5 ~ 100KGy; Described radiation field comprises gamma-radiation radiation field or electron beam irradiation field;
(3) take out in radiation chamber, obtain quaternary phosphine salt type cationic starch aqua; Further drying, obtains quaternary phosphine salt type cationic starch pulvis.
4. the preparation method of quaternary phosphine salt type cationic starch according to claim 1,2 or 3, it is characterized in that: described starch is a kind of in W-Gum, tapioca (flour), yam starch, green starch, sweet potato starch, sweet potato starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, or multiple.
5. the preparation method of quaternary phosphine salt type cationic starch according to claim 2, is characterized in that: described radical polymerization initiator is persulphate, ceric ammonium nitrate, persulphate-sulphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210043878.4A CN103289015B (en) | 2012-02-26 | 2012-02-26 | The preparation method of quaternary phosphine salt type cationic starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210043878.4A CN103289015B (en) | 2012-02-26 | 2012-02-26 | The preparation method of quaternary phosphine salt type cationic starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103289015A CN103289015A (en) | 2013-09-11 |
| CN103289015B true CN103289015B (en) | 2015-07-29 |
Family
ID=49090588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210043878.4A Expired - Fee Related CN103289015B (en) | 2012-02-26 | 2012-02-26 | The preparation method of quaternary phosphine salt type cationic starch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103289015B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674153A (en) * | 2017-10-12 | 2018-02-09 | 威尔（福建）生物有限公司 | A kind of auxiliary agent for improving greyness of paper and preparation method thereof |
| CN110194806B (en) * | 2019-05-21 | 2021-09-17 | 广西高源淀粉有限公司 | Preparation method of cationic starch |
| CN111549529B (en) * | 2020-05-12 | 2022-08-23 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111440278B (en) * | 2020-05-12 | 2022-09-27 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN113799514B (en) * | 2021-09-24 | 2022-07-22 | 广州松源实业有限公司 | Environment-friendly paper file box with mould proof and insect prevention functions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033230A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院上海药物研究所 | Cmptothecine derivative and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665554B (en) * | 2009-09-25 | 2011-05-04 | 上海大学 | Preparation method of cationic starch graft copolymer flocculant |
-
2012
- 2012-02-26 CN CN201210043878.4A patent/CN103289015B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033230A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院上海药物研究所 | Cmptothecine derivative and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103289015A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103289015B (en) | The preparation method of quaternary phosphine salt type cationic starch | |
| Raafat et al. | Radiation synthesis of superabsorbent CMC based hydrogels for agriculture applications | |
| CN105622847B (en) | A kind of synthetic method of water soluble chitosan-based flocculant and its application | |
| Zhang et al. | Preparation and swelling behaviors of a high temperature resistant superabsorbent using tetraallylammonium chloride as crosslinking agent | |
| CN103865083A (en) | Photosensitive hydrogel containing cyclodextrin and azobenzene and preparation method of photosensitive hydrogel | |
| CN106967217A (en) | Polyimidazole class compound and its in-situ preparation method and application | |
| CN108997504B (en) | Preparation method of ionic liquid functionalized cellulose carbamate material | |
| CN107574198B (en) | Method for preparing cyclodextrin inclusion complex carrier by alcohol precipitation grading | |
| Xu et al. | A first cyclodextrin-transition metal coordination polymer | |
| CN104448660A (en) | Superabsorbent resin as well as preparation method and applications thereof | |
| CN102585097A (en) | Method for preparing amphoteric starch | |
| CN103319661B (en) | Agarose-based dimethylpropiothetin acrylate grafted polymer and preparation method therefor | |
| CN103710016A (en) | Dry-powder structural fluid drag reducer and preparation method thereof | |
| CN107325301A (en) | A kind of high intensity γ polyglutamic acid hydrogels | |
| CN110511423A (en) | The method that double-template molecularly imprinted material on surface removes imidacloprid and Acetamiprid in water-soluble tea extract simultaneously | |
| Srivastava et al. | Solid state thermal degradation behaviour of graft copolymers of carboxymethyl cellulose with vinyl monomers | |
| CN103755841B (en) | A kind of Aminopyridine type acetyl synanthrin and preparation method thereof | |
| You et al. | Supramolecular linear polymer formed by host–guest interactions of β-cyclodextrin dimers and polyacrylamide end-capped with adamantane | |
| CN110025827B (en) | Water-retaining two-component hydrogel containing natural plant polysaccharide and preparation method and application thereof | |
| Doi et al. | Development of novel polymeric prodrugs synthesized by mechanochemical solid-state copolymerization of hydroxyethylcellulose and vinyl monomers | |
| CN113651927B (en) | Salt thickening polymer containing double-tail inner salt structure, and preparation method and application thereof | |
| CN109824824A (en) | One kind ionic liquid adsorbent of Type of Collective containing aminooimidazole and preparation method thereof | |
| CN109232616B (en) | (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof | |
| Singh et al. | Alumina supported synthesis of Cassia marginata gum‐g‐poly (acrylonitrile) under microwave irradiation | |
| CN105622846A (en) | Polymer water-absorbing resin preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 Termination date: 20160226 |